Dilute acid pretreatment of softwoods

Selective thinning of forests in the western United States will generate a large, sustainable quantity of softwood residues that can be an attractive feedstock for fuel ethanol production. The major species available from thinning of forests in northern California and the eastern Rocky Mountains include white fir (Abies concolor), Douglas fir (Pseudotsuga menziesii), and Ponderosa pine (Pinus ponderosa). Douglas fir chips were soaked in 0.4% sulfuric acid solution, then pretreated with steam at 200 – 230°C for 1 – 5 min. After pretreatment, 90 – 95% of the hemicellulose and as much as 20% of the cellulose was solubilized in water, and 90% of the remaining cellulose can be hydrolyzed to glucose by cellulase enzyme. The prehydrolysates, at as high as 10% total solid concentration, can be readily fermented by the unadapted yeastSaccharomyces cerevisiae D₅A.     

Electrochemical Synthesis of Tetrahexahedral Rhodium Nanocrystals with Extraordinarily High Surface Energy and High Electrocatalytic Activity

Noble metal nanocrystals (NCs) enclosed with high‐index facets hold a high catalytic activity thanks to the high density of low‐coordinated step atoms that they exposed on their surface. Shape‐control synthesis of the metal NCs with high‐index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high‐index facets through the dynamic oxygen adsorption/desorption mediated by square‐wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO.     

Catalytic Ethanolysis of Kraft Lignin into High‐Value Small‐Molecular Chemicals over a Nanostructured α‐Molybdenum Carbide Catalyst

We report the complete ethanolysis of Kraft lignin over an α‐MoC_1?x/AC catalyst in pure ethanol at 280 °C to give high‐value chemicals of low molecular weight with a maximum overall yield of the 25 most abundant liquid products (LP25) of 1.64 g per gram of lignin. The LP25 products consisted of C₆–C₁₀ esters, alcohols, arenes, phenols, and benzyl alcohols with an overall heating value of 36.5 MJ kg^?1. C₆ alcohols and C₈ esters predominated and accounted for 82 wt % of the LP25 products. No oligomers or char were formed in the process. With our catalyst, ethanol is the only effective solvent for the reaction. Supercritical ethanol on its own degrades Kraft lignin into a mixture of small molecules and molecular fragments of intermediate size with molecular weights in the range 700–1400, differing in steps of 58 units, which is the weight of the branched‐chain linkage C₃H₆O in lignin. Hydrogen was found to have a negative effect on the formation of the low‐molecular‐weight products.     

Intermetallic Pt2Si：magnetron-sputtering preparation and electrocatalysis toward ethanol oxidation

Although most transition metals have been tested as the promoter to Pt for electrocatalysis toward fuel cell reactions,semi-conductor elements,such as Si,have hitherto not been examined.Here we report a simple synthesis of intermetallic Pt2Si electrode using magnetron sputtering and the electrocatalysis toward ethanol oxidation reaction（EOR）.In comparison to Pt,the intermetallic Pt2Si surface turns out to be much more active in catalyzing the EOR：the onset potential shifts negatively by 150 mV,and the current density at 0.6 V increases by a magnitude of one order.Such an enormous enhancement in EOR catalysis is ascribed to the promotion effects of Si,which can not only provide active surface oxygenated species to accelerate the removal of COads,but also strongly alter the electronic property of Pt,as clearly indicated by the core-level shift in XPS spectrum.     

Four-Component Domino Reaction for the Synthesis of 1-(1H-Indol-2-yl)-1H-pyrazolo[1,2-b]phthalazine-5,10-diones

Facile, efficient, four-component domino reaction of dialkylphthalates, hydrazine hydrate, indole-3-carboxaldehydes, and malononitrile/ethyl cyanoacetate leads to the formation of 1-(1H-indol-2-yl)-1H-pyrazolo [1,2-b] phthalazine-5,10-diones in the presence of InCl₃ as catalyst in refluxing ethanol for 1 h in good yields. This four-component domino reaction transformation presumably proceeds via sequential addition, dehydration, condensation, and cyclization steps.     

Investigation into the structural composition of hydroalcoholic solutions as basis for the development of multiple suppression pulse sequences for NMR measurement of alcoholic beverages

An eight‐fold suppression pulse sequence was recently developed to improve sensitivity in ¹H NMR measurements of alcoholic beverages [Magn. Res. Chem. 2011 (49): 734–739]. To ensure that only one combined hydroxyl peak from water and ethanol appears in the spectrum, adjustment to a certain range of ethanol concentrations was required. To explain this observation, the structure of water–ethanol solutions was studied. Hydroalcoholic solutions showed extreme behavior at 25% vol, 46% vol, and 83% vol ethanol according to ¹H NMR experiments. Near‐infrared spectroscopy confirmed the occurrence of four significant compounds (‘individual’ ethanol and water structures as well as two water–ethanol complexes of defined composition – 1 : 1 and 1 : 3). The successful multiple suppression can be achieved for every kind of alcoholic beverage with different alcoholic strengths, when the final ethanol concentration is adjusted to a range between 25% vol and 46% vol (e.g. using dilution or pure ethanol addition). In this optimum region, an individual ethanol peak was not detected, because the ‘individual’ water structure and the 1 : 1 ethanol–water complex predominate. The nature of molecular association in ethanol–water solutions is essential to elucidate NMR method development for measurement of alcoholic beverages. The presented approach can be used to optimize other NMR suppression protocols for binary water–organic solvent mixtures, where hydrogen bonding plays a dominant role. Copyright © 2014 John Wiley & Sons, Ltd.     

聚乙二醇和液体石蜡介质对完全液相法制Cu-Zn-Al催化剂结构及CO加氢催化性能的影响

催化剂的形成和使用环境对催化剂的结构和性能会产生重要的影响.我们采用完全液相法,以PEG-400和液体石蜡分别作为热处理介质制备Cu-Zn-Al催化剂,用X射线粉末衍射、H2程序升温还原、N2吸附、X射线光电子能谱对其进行表征,考察热处理介质对催化剂结构的影响;以相应的热处理介质作为浆态床反应介质,考察介质对CO加氢催化反应性能的影响.结果表明,PEG-400作为热处理介质有助于提高催化剂的比表面积、Zn O的分散度和表面铜含量,催化剂中存在难还原的Cu+,有利于形成Cu+-Cu0之间的协同作用;在反应过程中,PEG-400作为反应介质可以抑制铜晶粒的长大,有利于乙醇的生成及C5烃选择性的提高,但催化剂的结构和表面组成会发生较大的变化.     

ESR and calculations on electronic structure of phenalenyl and phenalenyl derivative radicals

Calculations on electronic structure of the perinaphthenyl radical and phenalenyl derivative radicals responsible for the composition of the ESR spectrum of marine diesel under heating were performed to obtain support for the experimental ESR results. The parameters calculated were the hyperfine coupling constants (A), which were then used for comparison with the experimental data. The energy‐minimized structures were obtained using the density functional theory method. In all cases, the symmetry system was taken into account in theoretical calculations. The differences between experimental and theoretical values were below 7% for nearest hydrogens in molecules, named hyperfine coupling constant A (first neighbors) and 18% for farthest hydrogens atoms named hyperfine coupling constants A′ (second neighbors), for all structures analyzed. Copyright © 2014 John Wiley & Sons, Ltd.     

辛弗林衍生物的合成

以苯甲醚为起始原料,与乙酰氯发生付-克酰基化后脱甲基得到4-羟基苯乙酮,然后与液溴进行α-溴代得到2-溴-1-(4-羟苯基)乙酮,再与叔丁胺进行胺化得到1-(4-羟基苯基)-2-(叔丁基氨基)乙酮,最后用氢硼化钠还原合成目标产物1-(4-羟基苯基)-2-(叔丁基氨基)乙醇,总收率约为42.3%。     

全二维气相色谱-飞行时间质谱分析焦化柴油中饱和烃的分子组成

建立了全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)分析柴油馏分中饱和烃的分子组成的方法。结合谱库检索、质谱图解析、沸点与分子结构关系和全二维谱图特征,定性(或归类)了焦化柴油饱和烃组分中1057个化合物单体,其中正构烷烃排列规律性最强,一环~三环环烷烃按照极性和沸点的差异呈瓦片状分布在其上方。另外,还准确区分了在一维气相色谱上共流出的正构烷基环己烷和正构烷基环戊烷,以及正构 α 单烯烃。根据质谱采集的总离子流色谱图,采用峰面积归一化法得到了饱和烃组分的碳数分布结果,并将该方法应用于研究不同类型柴油馏分饱和烃的分子组成特点。结果表明,催化裂化和焦化柴油馏分饱和烃组分的化合物类型和分布各不相同。分子组成分析能为油品加工工艺机理的研究提供方法支持。